An online nano‐LC‐ESI‐FTICR‐MS method for comprehensive characterization of endogenous fragments from amyloid β and amyloid precursor protein in human and cat cerebrospinal fluid

Amyloid precursor protein (APP) is the precursor protein to amyloid β (Aβ), the main constituent of senile plaques in Alzheimer's disease (AD). Endogenous Aβ peptides reflect the APP processing, and greater knowledge of different APP degradation pathways is important to understand the mechanism underlying AD pathology. When one analyzes longer Aβ peptides by low‐energy collision‐induced dissociation tandem mass spectrometry (MS/MS), mainly long b‐fragments are observed, limiting the possibility to determine variations such as amino acid variants or post‐translational modifications (PTMs) within the N‐terminal half of the peptide. However, by using electron capture dissociation (ECD), we obtained a more comprehensive sequence coverage for several APP/Aβ peptide species, thus enabling a deeper characterization of possible variants and PTMs. Abnormal APP/Aβ processing has also been described in the lysosomal storage disease Niemann–Pick type C and the major large animal used for studying this disease is cat. By ECD MS/MS, a substitution of Asp7 → Glu in cat Aβ was identified. Further, sialylated core 1 like O‐glycans at Tyr10, recently discovered in human Aβ (a previously unknown glycosylation type), were identified also in cat cerebrospinal fluid (CSF). It is therefore likely that this unusual type of glycosylation is common for (at least) species belonging to the magnorder Boreoeutheria. We here describe a detailed characterization of endogenous APP/Aβ peptide species in CSF by using an online top‐down MS‐based method. Copyright © 2012 John Wiley & Sons, Ltd.     

Carbon dioxide reduction by an Al–O–P frustrated Lewis pair

The reaction of tBu₂P(O)H with Bis₂AlH (Bis = CH(SiMe₃)₂) afforded the adduct tBu₂P(H)–O–Al(H)Bis₂ (3). It slowly releases H₂ to form the first oxygen-bridged geminal Al/P frustrated Lewis pair tBu₂P–O–AlBis₂. It is capable of reversibly binding molecular hydrogen to afford 3, shown by NMR and H/D scrambling experiments, and forms a 1,2-adduct with CO₂. Importantly, the H₂ adduct 3 reduces CO₂ in a stoichiometric reaction leading to the formic acid adduct tBu₂P(H)–O–Al(CO₂H)Bis₂. The formation of the different species was explored by density functional theory calculations which provide support for the experimental results. All products were characterized by NMR spectroscopy as well as X-ray diffraction experiments and elemental analyses.

Addition vs. reduction: the geminal FLP Bis₂Al–O–PtBu₂ can reversibly bind molecular hydrogen, it reacts with CO₂ to give an adduct, and its hydrogen adduct reduces CO₂ to an adduct of formic acid.     

Homogeneous Reforming of Aqueous Ethylene Glycol to Glycolic Acid and Pure Hydrogen Catalyzed by Pincer-Ruthenium Complexes Capable of Metal–Ligand Cooperation

Glycolic acid is a useful and important α-hydroxy acid that has broad applications. Herein, the homogeneous ruthenium catalyzed reforming of aqueous ethylene glycol to generate glycolic acid as well as pure hydrogen gas, without concomitant CO₂ emission, is reported. This approach provides a clean and sustainable direction to glycolic acid and hydrogen, based on inexpensive, readily available, and renewable ethylene glycol using 0.5 mol % of catalyst. In-depth mechanistic experimental and computational studies highlight key aspects of the PNNH-ligand framework involved in this transformation.     

A Simple Nickel Catalyst Enabling an E-Selective Alkyne Semihydrogenation

Stereoselective alkyne semihydrogenations are attractive approaches to alkenes, which are key building blocks for synthesis. With regards to the most atom-economic reducing agent dihydrogen (H₂), only few catalysts for the challenging E-selective alkyne semihydrogenation have been disclosed, each with a unique substrate scope profile. Here, we show that a commercially available nickel catalyst facilitates the E-selective alkyne semihydrogenation of a wide variety of substituted internal alkynes. This results in a simple and broadly applicable overall protocol to stereoselectively access E-alkenes employing H₂, which could serve as a general method for synthesis.     

Magnetic dipole moments near Sn: Measurement on isomeric 11/2 states in odd-A Te and Te by NMR/ON

On-line low temperature nuclear orientation (OLNO) experiments have been performed on the odd-A Te isotopes ¹³¹Te and ¹³³Te using the technique of nuclear magnetic resonance on oriented nuclei (NMR/ON). The magnetic moments of the isomeric 11/2⁻ states have been measured extending the known data on these states in the Te isotopes up to the neutron shell closure at N = 82. The contribution to the 11/2⁻ magnetic moment in ¹³³Te due to core polarisation is calculated using an RPA shell model as well as corrections to the magnetic dipole operator caused by mesonic exchange currents. The neutron number dependence of the magnetic moments of the 11/2⁻ isomers in heavy Te isotopes is discussed in terms of particle-core coupling model (PCM) calculations.     

Densitometric quantification of individual phospholipids. Improvement and evaluation of a method using molybdenum blue reagent for detection

A densitometric method for simultaneous quantification of individual phospholipids based on visualization with molybdenum blue reagent is presented. Previously reported problems concerning colour instability have been solved. The method is specific for phosphorus-containing compounds and independent of the degree of fatty acid unsaturation. The molar absorptivities of most analysed phospholipids do not differ more than 10% from that for phosphatidylcholine from egg yolk. For cases of greater deviation (sphingomyelin, lysophosphatidylcholine and phosphatidylserine), analysis is accomplished by use of appropriate standard mixtures. The between-series coefficient of variation is ca. 9%. The method is compared to a preparative thin-layer chromatographic assay and another commonly used densitometric method.     

On two-scale convergence and related sequential compactness topics

A general concept of two-scale convergence is introduced and two-scale compactness theorems are stated and proved for some classes of sequences of bounded functions in L ²(Ω) involving no periodicity assumptions. Further, the relation to the classical notion of compensated compactness and the recent concepts of two-scale compensated compactness and unfolding is discussed and a defect measure for two-scale convergence is introduced.     

Thermoluminescence of YAG:Nd crystals coloured with x-rays

The spectral distribution of the thermoluminescence (TL) of YAG:Nd crystals coloured by x-ray irradiation at room temperature (RT) and at 80 K has been investigated. The spectral distribution of TL in the uv-, visible and near ir ranges shows that the energy transfer by bound exciton states (BES) to the RE³⁺ ions (Nd³⁺ and Tb³⁺) decreases with increasing temperature. The TL spectrum in the uv range is ascribed to the hole defect centers. Diminution of the energy transferred by the BES to the Nd³⁺ and Tb³⁺ ions is the direct cause for the occurrence of the group of lines ascribed to the Nd³⁺ ions in TL observed at LT, whereas at RT and higher only the groups of Tb lines are observed.     

Laser and radio-frequency spectroscopy of the 5d 36s 2 4 P 3/2,5/2 states in Ta I

The hyperfine structure of the metastable atomic states 5d ³6s ^{2 4} P _3/2 and⁴ P _5/2 in¹⁸¹Ta has been studied using high resolution laser spectroscopy and laser radio-frequency double-resonance methods.